An ab initio study of 1,5-suprafacial shifts in 5-substituted 1,3-cyclopentadienes (1,2)

Citation metadata

Date: Sept. 2005
From: Canadian Journal of Chemistry(Vol. 83, Issue 9)
Publisher: NRC Research Press
Document Type: Article
Length: 3,228 words

Document controls

Main content

Abstract :

A computational study of the degenerate 1,5-suprafacial migration of the 5-substituted cyclopentadienes is presented. The substituents considered are the Group 14-17 elements of the second through fifth periods, saturated by hydrogens as needed to fulfill normal valence requirements. The geometry of most transition states are remarkably similar in the carbon framework. The activation barrier to migration was shown to correlate well with a dimensionless "stretching" parameter, especially at the MP2 level. Key words: 5-substituted 1,3-cyclopentadiene, 1,2-haptotropic shift, 1,5-suprafacial shift, ab initio, transition states. Resume : On presente une etude theorique de la migration-1,5 suprafaciale de cyclopentadienes substitues en position 5. Les substituants consideres les elements 14 a 17 des periodes deux a cinq, satures par la quantite appropriee d'atomes d'hydrogene pour satisfaire leurs valences normales. Il est remarquable que la geometrie de la plupart des etats de transition est tres semblable a celle du squelette carbone. On a montre qu'il existe une bonne correlation entre la barriere d'activation a la migration et un parametre d'elongation sans dimension, particulierement au niveau MP2. Mots cles : cyclopenta-1,3-diene substitue en position 5, migration-1,2 haptotropique, migration-1,5 suprafaciale, ab initio, etats de transition. [Traduit par la Redaction]

Source Citation

Source Citation   

Gale Document Number: GALE|A141437265